DE10237992A1 - High strength plastically deformable molded body made from zirconium alloys, is used in the aircraft industry, space travel and as implants in medical applications - Google Patents
High strength plastically deformable molded body made from zirconium alloys, is used in the aircraft industry, space travel and as implants in medical applicationsInfo
- Publication number
- DE10237992A1 DE10237992A1 DE10237992A DE10237992A DE10237992A1 DE 10237992 A1 DE10237992 A1 DE 10237992A1 DE 10237992 A DE10237992 A DE 10237992A DE 10237992 A DE10237992 A DE 10237992A DE 10237992 A1 DE10237992 A1 DE 10237992A1
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- elements
- shaped body
- body according
- dendritic
- composition
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- Granted
Links
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 6
- 239000007943 implant Substances 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims description 8
- 210000001787 dendrite Anatomy 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000005300 metallic glass Substances 0.000 description 5
- 229910052790 beryllium Inorganic materials 0.000 description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910017870 Cu—Ni—Al Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UAIXRPCCYXNJMQ-RZIPZOSSSA-N buprenorphine hydrochlorie Chemical compound [Cl-].C([C@]12[C@H]3OC=4C(O)=CC=C(C2=4)C[C@@H]2[C@]11CC[C@]3([C@H](C1)[C@](C)(O)C(C)(C)C)OC)C[NH+]2CC1CC1 UAIXRPCCYXNJMQ-RZIPZOSSSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
Description
Die Erfindung betrifft hochfeste und bei Raumtemperatur plastisch verformbare berylliumfreie Formkörper aus Zirkonlegierungen. The invention relates to high-strength and at room temperature plastically deformable beryllium-free moldings Zirconium alloys.
Derartige Formkörper sind einsetzbar als hochbeanspruchte Bauteile z. B. in der Flugzeugindustrie, der Raumfahrt und der Fahrzeugindustrie, aber auch für medizintechnische Geräte und Implantate im medizinischen Bereich, wenn hohe Anforderungen an die mechanische Belastbarkeit, die Korrosionsbeständigkeit und die Oberflächenbeanspruchung insbesondere bei kompliziert geformten Bauteilen gestellt werden. Such moldings can be used as highly stressed Components z. B. in the aircraft industry, space travel and the automotive industry, but also for medical devices and implants in the medical field when high Mechanical strength requirements Corrosion resistance and surface stress especially in the case of complicated shaped components become.
Bekannt ist, dass bestimmte mehrkomponentige metallische Werkstoffe durch rasche Erstarrung in einen metastabilen glasartigen Zustand überführt werden können (metallische Gläser), um vorteilhafte (z. B. weichmagnetische, mechanische, katalytische) Eigenschaften zu erhalten. Meist sind diese Werkstoffe wegen der erforderlichen Abkühlrate der Schmelze nur mit geringen Abmessungen in mindestens einer Dimension z. B. dünne Bänder oder Pulver herstellbar. Damit sind sie als massiver Konstruktionswerkstoff nicht geeignet (siehe z. B. T. Masumoto, Mater. Sci. Eng. A179/180 (1994) 8-16). It is known that certain multi-component metallic Materials by rapid solidification into a metastable glassy state can be transferred (metallic Glasses) in order to obtain advantageous (e.g. soft magnetic, mechanical, catalytic) properties. Most of time are these materials because of the required cooling rate of the Melt only with small dimensions in at least one Dimension z. B. thin strips or powder can be produced. In order to they are not suitable as a solid construction material (see e.g. T. Masumoto, Mater. Sci. Eng. A179 / 180 (1994) 8-16).
Bekannt sind weiterhin bestimmte Zusammensetzungsbereiche mehrkomponentiger Legierungen, in denen solche metallische Gläser auch in massiver Form, z. B. mit Abmessungen > 1 mm, durch Gießverfahren hergestellt werden können. Solche Legierungen sind z. B. Pd-Cu-Si, Pd40Ni40P20, Zr-Cu-Ni-Al, La- Al-Ni-Cu (siehe z. B. T. Masumoto, Mater. Sci. Eng. A179/180 (1994) 8-16 und W. L. Johnson in Mater. Sci. Forum Vol. 225- 227, S. 35-50, Transtec Publications 1996, Switzerland). Also known are certain composition ranges of multi-component alloys, in which such metallic glasses also in solid form, e.g. B. with dimensions> 1 mm, can be produced by casting. Such alloys are e.g. B. Pd-Cu-Si, Pd 40 Ni 40 P 20 , Zr-Cu-Ni-Al, La-Al-Ni-Cu (see e.g. BT Masumoto, Mater. Sci. Eng. A179 / 180 (1994) 8 -16 and WL Johnson in Mater. Sci. Forum Vol. 225-227, pp. 35-50, Transtec Publications 1996, Switzerland).
Bekannt sind auch insbesondere berylliumhaltige metallische Gläser mit Zusammensetzungen der chemischen Formel (Zr1-xTix)a1 ETMa2 (Cu1-yNiy)b1LTMb2Bec, die in Abmessungen > 1 mm hergestellt werden können (A. Peker, W. L. Johnson, US-PS 5 288 344). Dabei bezeichnen die Koeffizienten a1. a2, b1, b2, c, x, y die Elementanteile in Atom-%, ETM ein frühes Übergangsmetall (Early Transition Metal) und LTM ein spätes Übergangsmetall (Late Transition Metal). Also known in particular are beryllium-containing metallic glasses with compositions of the chemical formula (Zr 1-x Ti x ) a1 ETM a2 (Cu 1-y Ni y ) b1 LTM b2 Be c , which can be produced in dimensions> 1 mm (A. Peker , WL Johnson, U.S. Patent 5,288,344). The coefficients denote a1. a2, b1, b2, c, x, y the element proportions in atomic%, ETM an early transition metal and LTM a late transition metal.
Weiterhin bekannt sind metallische Glas-Formkörper in allen ihren Dimensionen > 1 mm in bestimmten Zusammensetzungsbereichen der quinären Zr-Ti-Al-Cu-Ni-Legierungen (L. Q. Xing et al. Non-Cryst. Sol. 205-207 (1996) p. 579-601, presented at 9th Int. Conf. On Liquid and Amorphous Metals, Chicago, Aug. 27-Sep. 1, 1995; Xing et al., Mater. Sci. Eng. A 220 (1996) 155-161) und der pseudoquinären Legierung (Zr, Hf)a (Al, Zn)b (Ti, Nb)c (CuxFey (Ni, Co)z)d (DE 197 06 768 A1; DE 198 33 329 C2). Metallic glass moldings are also known in all their dimensions> 1 mm in certain composition ranges of the quinary Zr-Ti-Al-Cu-Ni alloys (LQ Xing et al. Non-Cryst. Sol. 205-207 (1996) p. .. 579-601, presented at Int Conf on 9 th Liquid and Amorphous Metals, Chicago, August 27-September 1, 1995;.. Xing et al, Mater Sci Eng A 220 (1996) 155-161)... and the pseudo-quinary alloy (Zr, Hf) a (Al, Zn) b (Ti, Nb) c (Cu x Fe y (Ni, Co) z ) d (DE 197 06 768 A1; DE 198 33 329 C2).
Es ist auch eine Zusammensetzung für eine mehrkomponentige berylliumhaltige Legierung mit der chemischen Formel (Zr100-a-bTiaNbb)75(BexCuyNiz)25 bekannt. Dabei bezeichnen die Koeffizienten a, b die Elementanteile in Atom-% mit a = 18,34; b = 6,66 und die Koeffizienten x, y, z bezeichnen die Verhältnisanteile in Atom-% mit x : y : z = 9 : 5 : 4. Diese Legierung ist zweiphasig, sie besitzt eine hochfeste, spröde glasartige Matrix und eine duktile, plastisch verformbare dendritische kubisch raumzentrierte Phase. Dadurch tritt eine erhebliche Verbesserung der mechanischen Eigenschaften bei Raumtemperatur ein, besonders im Bereich der makroskopischen Dehnung (C. C. Hays, C. P. Kim und W. L. Johnson, Phys. Rev. Lett. 84, 13, p, 2901-2904, (2000)). Ein gravierender Nachteil dieser Legierung besteht jedoch in der Verwendung des hoch toxischen Berylliums. A composition for a multi-component beryllium-containing alloy with the chemical formula (Zr 100-ab Ti a Nb b ) 75 (Be x Cu y Ni z ) 25 is also known. The coefficients a, b denote the element proportions in atomic% with a = 18.34; b = 6.66 and the coefficients x, y, z denote the proportions in atomic% with x: y: z = 9: 5: 4. This alloy is two-phase, it has a high-strength, brittle glass-like matrix and a ductile, plastically deformable dendritic cubic body-centered phase. This leads to a considerable improvement in the mechanical properties at room temperature, particularly in the area of macroscopic expansion (CC Hays, CP Kim and WL Johnson, Phys. Rev. Lett. 84, 13, p, 2901-2904, (2000)). A serious disadvantage of this alloy, however, is the use of the highly toxic beryllium.
Der Erfindung liegt die Aufgabe zugrunde, berylliumfreie hochfeste und plastisch verformbare Formkörper aus Zirkonlegierungen zur Verfügung zu stellen, die gegenüber den genannten metallischen Gläsern makroskopische Plastizität und Verformungsverfestigung bei Umformprozessen bei Raumtemperatur besitzen, ohne dass dadurch andere Eigenschaften, wie Festigkeit, elastische Dehnung oder das Korrosionsverhalten, wesentlich beeinträchtigt werden. The invention is based, beryllium-free the task high-strength and plastically deformable molded body To provide zirconium alloys that are superior to the mentioned metallic glasses macroscopic plasticity and Strain hardening in forming processes Have room temperature without causing others Properties such as strength, elastic elongation or that Corrosion behavior, are significantly impaired.
Diese Aufgabe wird mit den in den Patentansprüchen angegebenen hochfesten Formkörpern gelöst. This object is achieved with the in the claims specified high-strength moldings solved.
Die erfindungsgemäßen Formkörper sind dadurch gekennzeichnet,
dass sie aus einem Werkstoff bestehen, der in seiner
Zusammensetzung der Formel
Zra (E1)b (E2)c (E3)d (E4)e
entspricht, worin
E1 aus einem Element oder mehreren Elementen der mit
den Elementen Nb, Ta, Mo, Cr, W, Ti, V, Hf und Y
gebildeten Gruppe,
E2 aus einem Element oder mehreren Elementen der mit
den Elementen Cu, Au, Ag, Pd und Pt gebildeten
Gruppe,
E3 aus einem Element oder mehreren Elementen der mit
den Elementen Ni, Co, Fe, Zn und Mn gebildeten
Gruppe und
E4 aus einem Element oder mehreren Elementen der mit
den Elementen Al, Ga, Si, P, C, B, Sn, Pb und Sb
gebildeten Gruppe
besteht, mit
a = 100 - (b+c+d+e)
b = 5 bis 15
c = 5 bis 15
d = 0 bis 15
e = 5 bis 15
(a, b, c, d, e in Atom-%)
und mit gegebenenfalls geringen, herstellungstechnisch
bedingten Zusätzen und Verunreinigungen.
The moldings according to the invention are characterized in that they consist of a material which, in its composition, has the formula
Zr a (E1) b (E2) c (E3) d (E4) e
corresponds to what
E1 from one element or more elements of the group formed with the elements Nb, Ta, Mo, Cr, W, Ti, V, Hf and Y,
E2 from one or more elements of the group formed with the elements Cu, Au, Ag, Pd and Pt,
E3 from one or more elements of the group formed with the elements Ni, Co, Fe, Zn and Mn and
E4 from one or more elements of the group formed by the elements Al, Ga, Si, P, C, B, Sn, Pb and Sb
exists with
a = 100 - (b + c + d + e)
b = 5 to 15
c = 5 to 15
d = 0 to 15
e = 5 to 15
(a, b, c, d, e in atomic%)
and with possibly small, production-related additives and impurities.
Ein weiteres kennzeichnendes Merkmal besteht darin, dass die Formkörper ein homogenes mikrostrukturelles Gefüge besitzen, das aus einer glasartigen oder nanokristallinen Matrix mit darin eingebetteter duktiler dendritischer kubisch raumzentrierten Phase besteht, wobei mit einem geringen Volumenanteil von maximal 10% eine dritte Phase enthalten sein kann. Another characteristic is that the Molded articles have a homogeneous microstructural structure, with a glass-like or nanocrystalline matrix ductile dendritic cubic embedded therein body-centered phase, with a slight Volume fraction of maximum 10% contain a third phase can be.
Vorteilhaft ist es, wenn der Werkstoff für E1 das Element Nb, für E2 das Element Cu, für E3 das Element Ni und für E4 das Element Al enthält. It is advantageous if the material for E1 contains the element Nb, the element Cu for E2, the element Ni for E3 and the element for E4 Contains element Al.
Zur Realisierung besonders vorteilhafter Eigenschaften sollte der Werkstoff eine Zusammensetzung mit b = 6 bis 10, c = 6 bis 11, d = 0 bis 9 und e = 7 bis 12 aufweisen. To realize particularly advantageous properties the material has a composition with b = 6 to 10, c = 6 to 11, d = 0 to 9 and e = 7 to 12.
Vorteilhaft ist eine Zusammensetzung mit den Verhältnissen Zr : Nb = 5 : 1 bis 11 : 1 sowie Zr : Al = 6 : 1 bis 9 : 1. A composition with the ratios is advantageous Zr: Nb = 5: 1 to 11: 1 and Zr: Al = 6: 1 to 9: 1.
Die im Werkstoff enthaltene dendritisch kubisch raumzentrierten Phase sollte vorteilhaft eine Zusammensetzung mit b = 7 bis 15, c = 3 bis 9, d = 0 bis 3 und e = 7 bis 10 aufweisen (Zahlenangaben in Atom-%). The dendritic cubic contained in the material body centered phase should advantageously be a composition with b = 7 to 15, c = 3 to 9, d = 0 to 3 and e = 7 to 10 have (figures in atomic%).
Ein Werkstoff mit besonders guten Eigenschaften besteht aus Zr66,4Nb6,4Cu10,5Ni8,7Al8 (Zahlenangaben in Atom- %). A material with particularly good properties consists of Zr 66.4 Nb 6.4 Cu 10.5 Ni 8.7 Al 8 (figures in atomic%).
Ein weiterer Werkstoff mit besonders guten Eigenschaften besteht aus Zr71Nb9Cu8Ni1Al11 (Zahlenangaben in Atom- %). Another material with particularly good properties consists of Zr 71 Nb 9 Cu 8 Ni 1 Al 11 (figures in atomic%).
Der Volumenanteil der gebildeten dendritischen kubisch raumzentrierter Phase in der Matrix beträgt erfindungsgemäß 25% bis 95%, vorzugsweise 50% bis 95%. The volume fraction of the dendritic cubic formed The body-centered phase in the matrix is according to the invention 25% to 95%, preferably 50% to 95%.
Die Länge der Primär-Dendritenachsen liegt im Bereich von 1 µm bis 100 µm und der Radius der Primär-Dendriten beträgt 0,2 µm bis 2 µm. The length of the primary dendrite axes is in the range of 1 µm to 100 µm and the radius of the primary dendrites is 0.2 µm to 2 µm.
Zur Herstellung der Formkörper wird durch Gießen der Zirkon- Legierungsschmelze in eine Kupferkokille ein Halbzeug oder das fertige Gußteil hergestellt. To manufacture the molded bodies, the zirconium Alloy melts into a copper mold or a semi-finished product the finished casting is made.
Der Nachweis der dendritischen kubisch raumzentrierter Phase in der glasartigen oder nanokristallinen Matrix und die Bestimmung der Größe und des Volumenanteils der dendritischen Ausscheidungen kann über Röntgenbeugung, Rasterelektronenmikroskopie oder Transmissionselektronenmikroskopie erfolgen. Evidence of the dendritic cubic body-centered phase in the glassy or nanocrystalline matrix and the Determination of the size and volume fraction of the dendritic Excretions can be via x-ray diffraction, Scanning electron microscopy or Transmission electron microscopy.
Die Erfindung ist nachstehend anhand von Ausführungsbeispielen näher erläutert. The invention is based on Embodiments explained in more detail.
Eine Legierung mit der Zusammensetzung Zr71Nb9Cu8Ni1Al11 (Zahlenangaben in Atom-%) wird in eine zylinderförmige Kupferkokille mit Innendurchmesser 5 mm abgegossen. Der erhaltene Formkörper besteht aus einer glasartigen Matrix und darin eingebetteter duktiler kubisch raumzentrierter Phase. Der Volumenanteil der dendritischen Phase beträgt ca. 50%. Dadurch wird eine Bruchdehnung von 3,5% bei einer Bruchfestigkeit von 1791 MPa erreicht. Die elastische Dehnung an der technischen Streckgrenze (0,2% Dehngrenze) beträgt 2,5% bei einer Festigkeit von 1638 MPa. Der Elastizitätsmodul beträgt 72 GPa. An alloy with the composition Zr 71 Nb 9 Cu 8 Ni 1 Al 11 (figures in atomic%) is poured into a cylindrical copper mold with an inner diameter of 5 mm. The molded body obtained consists of a glass-like matrix and embedded ductile, cubic, body-centered phase. The volume fraction of the dendritic phase is approximately 50%. This results in an elongation at break of 3.5% with a breaking strength of 1791 MPa. The elastic elongation at the technical yield strength (0.2% yield strength) is 2.5% with a strength of 1638 MPa. The modulus of elasticity is 72 GPa.
Eine Legierung mit der Zusammensetzung Zr71Nb9Cu8Ni1Al11 (Zahlenangaben in Atom-%) wird in eine zylinderförmige Kupferkokille mit Innendurchmesser 3 mm abgegossen. Der erhaltene Formkörper besteht aus einer nanokristallinen Matrix und darin eingebetteter duktiler kubisch raumzentrierter Phase. Der Volumenanteil der dendritischen Phase beträgt ca. 95%. Dadurch wird eine Bruchdehnung von 5,4% bei einer Bruchfestigkeit von 1845 MPa erreicht. Die elastische Dehnung an der technischen Streckgrenze (0,2% Dehngrenze) beträgt 1,5% bei einer Festigkeit von 1440 MPa. Der Elastizitätsmodul beträgt 108 GPa. An alloy with the composition Zr 71 Nb 9 Cu 8 Ni 1 Al 11 (figures in atomic%) is poured into a cylindrical copper mold with an inner diameter of 3 mm. The molded body obtained consists of a nanocrystalline matrix and a ductile, cubic, body-centered phase embedded therein. The volume fraction of the dendritic phase is approximately 95%. This results in an elongation at break of 5.4% with a breaking strength of 1845 MPa. The elastic elongation at the technical yield strength (0.2% yield strength) is 1.5% with a strength of 1440 MPa. The modulus of elasticity is 108 GPa.
Eine Legierung mit der Zusammensetzung Zr66,4Nb4,4Mo2Cu10,5Ni8,7Al8 (Zahlenangaben in Atom- %) wird in eine zylinderförmige Kupferkokille mit Innendurchmesser 5 mm abgegossen. Der erhaltene Formkörper besteht aus einer glasartigen Matrix und darin eingebetteter duktiler kubisch raumzentrierter Phase. Der Volumenanteil der dendritischen Phase beträgt ca. 50%. Dadurch wird eine Bruchdehnung von 3, 4% bei einer Bruchfestigkeit von 1909 MPa erreicht. Die elastische Dehnung an der technischen Streckgrenze (0,2% Dehngrenze) beträgt 2,1% bei einer Festigkeit von 1762 MPa. Der Elastizitätsmodul beträgt 94 GPa. An alloy with the composition Zr 66.4 Nb 4.4 Mo 2 Cu 10.5 Ni 8.7 Al 8 (numbers in atom%) is poured into a cylindrical copper mold with an inner diameter of 5 mm. The molded body obtained consists of a glass-like matrix and embedded ductile, cubic, body-centered phase. The volume fraction of the dendritic phase is approximately 50%. An elongation at break of 3.4% is achieved with a breaking strength of 1909 MPa. The elastic elongation at the technical yield strength (0.2% yield strength) is 2.1% with a strength of 1762 MPa. The modulus of elasticity is 94 GPa.
Beispiel 4Example 4
Eine Legierung mit der Zusammensetzung Zr70Nb10,5Cu8Co2Al9,5 (Zahlenangaben in Atom-%) wird in eine zylinderförmige Kupferkokille mit Innendurchmesser 3 mm abgegossen. Der erhaltene Formkörper besteht aus einer nanokristallinen Matrix und darin eingebetteter duktiler kubisch raumzentrierter Phase. Der Volumenanteil der dendritischen Phase beträgt ca. 95%. Dadurch wird eine Bruchdehnung von 6,2% bei einer Bruchfestigkeit von 1680 MPa erreicht. Die elastische Dehnung an der technischen Streckgrenze (0,2% Dehngrenze) beträgt 1,9% bei einer Festigkeit von 1401 MPa. Der Elastizitätsmodul beträgt 84 GPa. An alloy with the composition Zr 70 Nb 10.5 Cu 8 Co 2 Al 9.5 (figures in atomic%) is poured into a cylindrical copper mold with an inner diameter of 3 mm. The molded body obtained consists of a nanocrystalline matrix and a ductile, cubic, body-centered phase embedded therein. The volume fraction of the dendritic phase is approximately 95%. An elongation at break of 6.2% is achieved with a breaking strength of 1680 MPa. The elastic elongation at the technical yield strength (0.2% yield strength) is 1.9% with a strength of 1401 MPa. The modulus of elasticity is 84 GPa.
Claims (9)
Zra (E1)b (E2)c (E3)d (E4)e
entspricht, worin
E1 aus einem Element oder mehreren Elementen der mit den Elementen Nb, Ta, Mo, Cr, W, Ti, V, Hf und Y gebildeten Gruppe,
E2 aus einem Element oder mehreren Elementen der mit den Elementen Cu, Au, Ag, Pd und Pt gebildeten Gruppe,
E3 aus einem Element oder mehreren Elementen der mit den Elementen Ni, Co, Fe, Zn und Mn gebildeten Gruppe und
E4 aus einem Element oder mehreren Elementen der mit den Elementen Al, Ga, Si, P, C, 8, Sn, Pb und Sb gebildeten Gruppe
besteht, mit
a = 100 - (b+c+d+e)
b = 5 bis 15
c = 5 bis 15
d = 0 bis 15
e = 5 bis 15
(a, b, c, d, e in Atom-%)
und mit gegebenenfalls geringen, herstellungstechnisch bedingten Zusätzen und Verunreinigungen, und dass die Formkörper ein homogenes mikrostrukturelles Gefüge besitzen, das aus einer glasartigen oder nanokristallinen Matrix mit darin eingebetteter duktiler dendritischer kubisch raumzentrierten Phase besteht, wobei mit einem geringen Volumenanteil von maximal 10% eine dritte Phase enthalten sein kann. 1. High-strength, plastically deformable beryllium-free moldings made of zirconium alloys, characterized in that the moldings consist of a material which, in its composition, has the formula
Zr a (E1) b (E2) c (E3) d (E4) e
corresponds to what
E1 from one or more elements of the group formed with the elements Nb, Ta, Mo, Cr, W, Ti, V, Hf and Y,
E2 from one or more elements of the group formed with the elements Cu, Au, Ag, Pd and Pt,
E3 from one or more elements of the group formed with the elements Ni, Co, Fe, Zn and Mn and
E4 from one or more elements of the group formed with the elements Al, Ga, Si, P, C, 8, Sn, Pb and Sb
exists with
a = 100 - (b + c + d + e)
b = 5 to 15
c = 5 to 15
d = 0 to 15
e = 5 to 15
(a, b, c, d, e in atomic%)
and with possibly small, production-related additives and impurities, and that the moldings have a homogeneous microstructural structure consisting of a glass-like or nanocrystalline matrix with a ductile dendritic cubic body-centered phase embedded therein, a third phase with a small volume fraction of at most 10% may be included.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10237992A DE10237992B4 (en) | 2001-08-30 | 2002-08-12 | High-strength, at room temperature plastically deformable beryllium-free shaped body of zirconium alloys |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10143683 | 2001-08-30 | ||
| DE10143683.1 | 2001-08-30 | ||
| DE10218281 | 2002-04-19 | ||
| DE10218281.7 | 2002-04-19 | ||
| DE10237992A DE10237992B4 (en) | 2001-08-30 | 2002-08-12 | High-strength, at room temperature plastically deformable beryllium-free shaped body of zirconium alloys |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE10237992A1 true DE10237992A1 (en) | 2003-03-27 |
| DE10237992A9 DE10237992A9 (en) | 2004-09-09 |
| DE10237992B4 DE10237992B4 (en) | 2006-10-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| DE10237992A Expired - Fee Related DE10237992B4 (en) | 2001-08-30 | 2002-08-12 | High-strength, at room temperature plastically deformable beryllium-free shaped body of zirconium alloys |
| DE50213552T Expired - Lifetime DE50213552D1 (en) | 2001-08-30 | 2002-08-12 | E BERYLIUM-FREE FORM BODY OF CIRCON ALLOYS |
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| Application Number | Title | Priority Date | Filing Date |
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| DE50213552T Expired - Lifetime DE50213552D1 (en) | 2001-08-30 | 2002-08-12 | E BERYLIUM-FREE FORM BODY OF CIRCON ALLOYS |
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| Country | Link |
|---|---|
| US (1) | US7300529B2 (en) |
| EP (1) | EP1423550B1 (en) |
| JP (1) | JP4338515B2 (en) |
| KR (1) | KR20040027897A (en) |
| CN (1) | CN1549868B (en) |
| AT (1) | ATE431438T1 (en) |
| CA (1) | CA2458516A1 (en) |
| DE (2) | DE10237992B4 (en) |
| DK (1) | DK1423550T3 (en) |
| WO (1) | WO2003025242A1 (en) |
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-
2002
- 2002-08-12 DE DE10237992A patent/DE10237992B4/en not_active Expired - Fee Related
- 2002-08-12 EP EP02754540A patent/EP1423550B1/en not_active Expired - Lifetime
- 2002-08-12 KR KR10-2004-7002368A patent/KR20040027897A/en not_active Application Discontinuation
- 2002-08-12 AT AT02754540T patent/ATE431438T1/en not_active IP Right Cessation
- 2002-08-12 DE DE50213552T patent/DE50213552D1/en not_active Expired - Lifetime
- 2002-08-12 CA CA002458516A patent/CA2458516A1/en not_active Abandoned
- 2002-08-12 WO PCT/DE2002/003030 patent/WO2003025242A1/en active Application Filing
- 2002-08-12 DK DK02754540T patent/DK1423550T3/en active
- 2002-08-12 US US10/487,383 patent/US7300529B2/en not_active Expired - Fee Related
- 2002-08-12 JP JP2003530011A patent/JP4338515B2/en not_active Expired - Fee Related
- 2002-08-12 CN CN028169476A patent/CN1549868B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1549868A (en) | 2004-11-24 |
| EP1423550B1 (en) | 2009-05-13 |
| US20040238077A1 (en) | 2004-12-02 |
| EP1423550A1 (en) | 2004-06-02 |
| JP2005502788A (en) | 2005-01-27 |
| ATE431438T1 (en) | 2009-05-15 |
| DE10237992A9 (en) | 2004-09-09 |
| CN1549868B (en) | 2010-05-26 |
| DE10237992B4 (en) | 2006-10-19 |
| KR20040027897A (en) | 2004-04-01 |
| DK1423550T3 (en) | 2009-08-03 |
| CA2458516A1 (en) | 2003-03-27 |
| DE50213552D1 (en) | 2009-06-25 |
| JP4338515B2 (en) | 2009-10-07 |
| WO2003025242A1 (en) | 2003-03-27 |
| US7300529B2 (en) | 2007-11-27 |
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